Resole varnishes prepared from substituted phenols

ABSTRACT

The invention relates to resole resin varnishes in largely nonaqueous organic solvents, especially lower alkanols. The resole resins are produced by reacting, under basic aqueous conditions, formaldehyde with a phenol mixture which has been prepared by partial alkylation of phenol with a specific mixture of carbocyclic compounds containing between eight and 13 carbon atoms. The resulting resole resin is then dissolved in organic solvent. The resulting solutions are useful as varnishes in the manufacture of impregnated sheets, laminates, and other reinforced plastics.

United States Patent Anderson et al.

REsoLE vARNIsnEs PREPARED FROM SUBSTITUTED PHENOLS Inventors; George J.Anderson, Wilbraham,

' Mass. 01095; Ronald H. Dahms,

Springfield, Mass. 01 106 Assignee: Monsanto Company, St. Louis, Mo.

Filed: March 9, 1971 App1.No.: 122,525

Related US. Application Data Continuation-impart of Ser. No. 588,310,Oct. 21, 1966, abandoned, and a continuation-inpart of Ser. No. 676,043,Oct. 18, 1967, abandoned, and a continuation-in-part of Ser. No.738,812, June 21, 1968, abandoned.

US. Cl. ..260/29.3, 117/124 E, 117/1 38.8 A, 117/143 A, 117/155 L,117/161 L,'161/198, 161/205, 161/227, 161/257, 161/264,

260/31.4 R, 260/328 R, 260/33.6 R, 260/51 Int. Cl. ..C09g 5/08, C08g 37/10, C08g 51/34 Field of Search ..260/29.3, 53 R References Cited UNITEDSTATES PATENTS 4/1939 Zinke .....26 0/6 24 51 Sept. 12, 1972 2,388,583ll/l945 Ward ..260/6l9 2,388,584 11/1945 Ward ..260/6l9 2,423,4l5 7/1947Soday ..260/6 1 9 2,444,233 6/ 1948 Soday ..260/6 19 2,824,860 2/ 1958Aldridge et al ..260/82 3,420,915 l/ l 969 Braithwaite ..260/ 8373,526,677 9/1970 Dahms et a1. ..260/53 X Prir riiiry Examinerl*loward E.Schain AttorneyJohn W. Klooster, James C. Logomasini, Richard W.Sternberg and Neal E. Willis [57] ABSTRACT The invention relates toresole resin varnishes in large- 1y non-aqueous organic solvents,especially lower al- 9 Claims, No Drawings RESOLE VARNISHES PREPAREDFROM SUBSTITUTED PHENOLS RELATED APPLICATIONS This application is acontinuation-in-part of our earlier filed US. patent applications, Ser.No. 588,3 l0, filed Oct. 21, 1966 now abandoned, Ser. No. 676,043, filedOct. 18, 1967 now abandoned, and Sen No. 738,812, filed June 21, 1968now abandoned.

BACKGROUND Phenolic varnishes using phenol-aldehyde resole type resinshave long been used to impregnate cellulosic and other woven andnon-woven materials, especially in fibrous sheet form, and to preparelaminates thereof. However, resole resin varnishes heretofore known whencured have generally suffered from a lack of properties for certainapplications, forexample, electrical properties, water resistanceproperties, and mechanical strength properties. Because of thesedeficiencies, there has been along felt need in the art of resole resinvarnishes for modified phenol-aldehyde resole resins which wouldovercome one or more of these deficiencies.

One approach to producing modified phenol-aldehyde'resins has involvedusing as starting materials for reaction with aldehydes substitutedphenols so as to produce phenol-aldehyde resins having a high molecularweight in proportion to the total amount of phenol used in resinmanufacture. The ratio of resole resin prepolymer molecular weight(before curing) to starting phenol content can be termed, forconvenience purposes, the PMW efficiency.

In the past, increases in PMW efficiency have been attempted either byusing naturally occurring substituted phenols, for example, cresol orcresylic acid, or by using synthetically substituted phenols includingnaturally occurring drying oils (such as tung oil or oiticica oil),terpenes, and various unsaturated hydrocarbon materials (such asstyrene). Phenol-aldehyde resins made from phenols substituted withthese starting materials, however, have a plurality of disadvantages.For one thing, the cost of starting materials is so significant that thecost of the resulting phenol-aldehyde resin is increased to the pointwhere it is not competitive with other polymeric materials as respectsmany use applications. In addition, the resulting phenol-aldehydeproduct when cured either has an undesirably wide distribution ofphysical and chemical properties (perhaps caused by using a substitutedphenol mixture in which the substituents vary widely from one anotherstructurally), or has an undesirably narrow distribution of physical andchemical properties (perhaps caused by using a substituted phenol inwhich the substitutents vary only slightly or even not at all from oneanother structurally). Furthermore, even though the PMW efficiency isimproved by using such prior art substituted phenols, the phenolicproduct resole resins derived therefrom tend to be inferior as respectssuch properties as storage stability, viscosity, cure rate, or necessityfor close manufacturing tolerances.

It has now been discovered that when one reacts an aldehyde with aphenol which has been synthetically substituted with a certainwell-defined mixture of C5 through C carbocyclic compounds, there isproduced a phenol-aldehyde resole resin product which has a high PMWefficiency. When such resole resin product is used as the resincomponent in a varnish, the resulting novel varnish has the capacity,when used in the manufacture of laminates, to produce when thermoset, anexcellent combination of electrical, mechanical, and water resistanceproperties. These varnishes can contain resin solids which areadvanceable to a greater extent without forming precipitates from thevarnish organic solvent phase than is the case with aqueous solutions ofthese new phenol-aldehyde resole resin products.

When such substituted phenol-aldehyde (especially one usingformaldehyde) resole resin is made into a varnish, such varnish has goodstorage stability and low viscosity characteristicsproperties desirablein phenolic varnishes intended for use in laminate manufacture. Thus,resulting varnishes are useful for impregnating a preformed integralsheet of fibrous cellulosic material, such as cloth, paper, asbestos,and the like, and for making laminates thereof. These end products havegenerally improved properties heretofore unknown. For example, such aproduct laminate gives surprisingly and unexpectedly a combination ofbetter electrical, mechanical, water absorption properties than knownprior art laminates. Such resole resins themselves, when thermoset,characteristically have surprisingly lower glass transition temperaturesthan resole resins made, say, from an aldehyde and a substituted phenol,such as cresol.

SUMMARY This invention is directed to varnishes of certainphenol-aldehyde resole resins in organic solvents. These varnishes areespecially adapted for use in the manufacture of impregnated sheetmaterials and of laminates thereof. The products have high flexuralstrength, low water absorption and excellent electrical properties.These varnishes display excellent penetration qualities as respectsnon-woven, sheet-like materials.

The varnishes of this invention comprise:

. A. from about 20 to weight percent of a dissolved mixture of aphenol-formaldehyde resole resin,

B. from about 0.5 to 15 weight percent of dissolved water,

C. the balance up to weight percent of any given varnish being anorganic liquid which:

1. is substantially inert (as respects such resin and water,

2. evaporates below about C. at atmospheric pressures,

3. is a mutual solvent for said resole resin and said water (ifpresent), the amount of said organic liquid being present in any givenvarnish being such as to maintain both said resole resin and said waterin dissolved form.

The phenol-formaldehyde resole resin employed in the products of thisinvention has a formaldehyde to phenol mol ratio of from about 0.8 to2.0 (preferably from about 0.9 to 1.5), and is produced by reacting, inthe presence of a basic organic catalyst under liquid aqueous phaseconditions, a certain substituted phenol mixture with formaldehyde. Theresole resin used in this invention further has a relatively highmolecular weight as shown by the fact that it is substantiallywater-insoluble, but it also has a methanol solubility such that a 60weight percent solution thereof can be prepared in methanol. Suchmethanol solution characteristically has a viscosity not greater thanabout 5,000 centipoises, and preferably this viscosity lies in the rangefrom about 50 to 500 centipoises. In addition, this resin has a freeformaldehyde content which is less than about 5 weight percent (based ontotal dry resin weight).

The substituted phenol mixture used to make such resin is itselfprepared by reacting phenol under Friedel-Crafts conditions with acontrolled mixture of carbocyclic compounds. The mixture of carbocycliccompounds comprises (on a 100 weight per cent basis when in a formsubstantially free of other materials):

A. from about 10 through 40 weight percent of compounds each molecule ofwhich has:

1. the indene nucleus,

2. from nine through 13 carbon atoms,

3. as nuclear substituents from through 4 methyl groups,

B. from about 5 through 70 weight percent of compounds each molecule ofwhich has:

1. the dicyclopentadiene nucleus,

2. from about through 13 carbon atoms,

3. as nuclear substituents from 0 through 3 methyl groups,

C. from about 15 through 65 weight percent of compounds each molecule ofwhich has:

1. a phenyl group substituted by a vinylidene group,

2. from about eight through 13 carbon atoms,

3. as substituents from 0 through 3 groups selected from the classconsisting of methyl and ethyl,

D. from about 0 through 5 weight percent divinyl benzene,

E. provided that the sum total of all such compounds in any given suchmixture of carbocyclic compounds is always 100 weight percent.

At the time when such controlled mixture of carbocyclic compounds isreacted with phenol as indicated, there can be present in such mixtureas diluents inert (i.e. as respects reactivity towards phenol underFriedel-Crafts reaction conditions) organic compounds such as aromaticand aliphatic hydrocarbons. Thus, there is present, conveniently, atleast about 25 weight percent of diluent in such total combination ofmixture of carbocyclic compounds and diluent, although this value isvariable depending upon reactants and reaction conditions. While thereis no apparent upper limit on the amount of diluent present, it ispreferred that the amount of diluent present be not greater than about95 weight percent (same basis). Preferably, the amount of diluent rangesfrom about 15 to 70 weight percent (same basis). Up to about 10 weightpercent (same basis) of water can be present, but it is preferred to usesubstantially anhydrous conditions.

Carbocyclic compound mixtures useful in this invention are availablecommercially from various petroleum producers under a variety of tradenames. For example, one suitable carbocyclic compound mixture isavailable from Enjay Chemical Company under the 6 trade designationHeart Cut LPD. Another suitable such mixture is available from MonsantoCompany, St.

Louis, Missouri, under the trade designation "Resin Oil. Still anothersuch mixture is available from the Gulf Oil Company under the tradedesignation Resin Former Feed Stock. A presently preferred such mixtureis the Monsanto Company Resin Oil which is a C to C product cut with aboiling range of from about 300 to 425F. (150 to about 220C.) andcontains the indicated carbocyclic compound mixture. Shown below inTable l is a breakdown such as is made by vapor phase chromatographyshowing composition of these three carbocyclic compound mixtures:

TABLE I Carbocyclic Compounds Gulf Oil Monsanto Enjay vinylideneAromatics Styrene C, 7.6 1.4 10.1 Alpha-methylstyrenc C, 1.6 2.8 2.2Beta-methylstyrene C, 1.5 1.6 2.1 Vinyltoluene C 4.5 17.4 10.5 C,Alkylstyrene C 0.9 6.2 5.8 Divinyl benzene C 0.3 1.3 1.6 lndenes lndeneC, 12.7 17.6 12.7 Methylindene C 0.3 5.5 7.6 Cyclopentadieneslsoprene-cyclopentadiene C 0.6 0.3 Dicyclopentadiene C 42.7 13.9 1.1Methylcyclopentadiene C 12.4 4.6 2.1 Diluents Alkyl Aromatics Benzene C,0.5 0.1 Toluene C, 3.9 0.8 C Alkylbenzene C 7.4 0.4 12.1 C AlkylbenzeneC, 1.2 19.2 22.2 C, Alkylbenzene C 4.1 6.3 Naphthalenes Naphthalene C0.2 3 2 2.2 Unidentified (Aliphatics) 2.1 Total Carbocyclic Compoundmixture content 84.8 72.6 55.9 ASTM Boil Range, F.

(ASTM D-86) Initial boiling point 283 315 307 10% 318 333 320 50% 329343 342 90% 348 367 401 End point 364 402 41 l Residue 1.0 SpecificGravity 0.952 0.933 0.909

L6 Footnotes for Table 1 L6 This styrene compound is selected from thegroup consisting of ethyl-styrene and dimethylstyrene. L6 Availablecommercially from the Gulf Oil Company as Resin Former Feed Stock. L6Available commercially from the Monsanto Company under the tradedesignation Resin Oil. L6 Available commercially from Enjay Companyunder the trade designation Heart Cut LPD.

By the term dicylopentadiene reference is had 0 a molecule having thestructure:

CH\ o 1 CHCH H CH2 1 11 al/ s 2 CH CH2 By the phase when in a formsubstantially free of other materials reference is had to a mixture(e.g. of starting materials, of products, or the like, as the case maybe) which is substantially free (e.g. on an analytical or a theoreticalbasis) of substances (like inerts) other than such mixture itself. Forexample, in Table I above, the carbocyclic compound mixtures arecomposed of indenes, vinylidene aromatics, and dicyclopentadienes aswell as inert diluents, such as alkyl aromatics, naphthalenes andunidentified aliphatics, but each contains a combination (on a 100weight percent basis in a form substantially free of other materials) ofcomponents (indenes, dicyclopentadiene, and vinylidene aromatics) asdescribed above.

To react phenol with such an aforedescribed carbocyclic compoundmixture, it is convenient to use Friedel-Crafts conditions, as indicatedThe term Friedel-Crafts conditions as used herein refers to theconventional conditions known to those of ordinary skill in the art usedfor the alkylating or arylating of hydrocarbons (including phenol) bythe catalytic action of aluminum chloride or equivalent acid catalyst inthe presenceof appropriate 'Iiea't and pressure. In the practiceof thisinvention the phenol and suitable Friedel-Crafts acid catalyst, aremixed, broughtto the proper'tempera'ture, and the carbocyclic compoundmixture metered into the acidified (or catalyzed) phenol.

For purposes of this invention, the reaction of carbocyclic compoundmixture with phenol is preferably carried out at temperatures in therange of from about 25' to 200C., although higher and lower temperaturescan be used. Also, the reaction is preferably conducted under liquidphase conditions at or below atmospheric pressures althoughsuperatmospheric pressures can be used. Inert hydrocarbons, as indicatedabove, generally facilitate the process. Such inert hydrocarbons can bereadily removed, such as by vacuum stripping, at the completion of thereaction if desired. Especially when stripping is contemplated, the mostpreferred inert hydrocarbons have boiling points between about 70 and140C. The progress of the reaction can be monitored, if desired, bymeasuring the quantity remaining of unreactedcarbocyc'lic compoundmixture using, fo example, vapor phase chromotography.

Friedel-Craftscatalysts which may be used in place of aluminum chloride,or together with aluminum chloride, include:

A. other inorganic halides, such as gallium, titanium,

antimony and zinc halides (including ZnCl B. inorganic acids such assulphuric, phosphoric and the hydrogen halides (including HF);

C. activated clays, silica gel and alumina;

D. BE, and BF organic complexes, such as com plexes of BF with organiccompounds, such as ethanol, butanol, glycol, phenol, cresol, anisole,ethyl ether, isopropyl ether, di-n-butyl ether, formic acid, aceticacid, propionic acid and the like, or with inorganic acids, such asphosphoric acid,

sulfuric acid, and the like, and

E. alkyl, aryl and aralkyl sulfonic acids, such as ethanesulfonic acid,benzene sulfonic acid, benzene disulfonic acid, chlorobenzene sulfonicacid, 3,4-dichlorobenzene sulfonic acid, cresol sulfonic acids, phenolsulfonic acids, toluene sulfonic acids, xylene sulfonic acids,octylphenol sulfonic acid, B-naphthalene sulfonic acid, l-naphthol-4-sulfonic acid, and the like.

When BF as such, is employed, it is conveniently fed to a reactionmixture in gaseous form.

While any combination of carbocyclic compound starting mixture, phenol,and catalyst can be used, it is particularly convenient to react phenolwith carbocyclic compound mixture in the presence of less than about 10weight percent (based on the starting phenol) of acid catalystTypically, from about 0.1 to 1 weight percent of Friedel-Crafts acidcatalyst is employed (based on phenol).

The reaction mass is heated to a temperature in the range of from about25 to 200 C. The rate of this reaction is dependent to some degree onthe temperature employed. In general, the reaction is rapid, and acomplete reaction between phenol and carbocyclic compound mixture ispreferred. Generally, a total heating time of from about 10 minutes to 4hours is employed. The various process variables are summarized in TableII below.

Total carbocyclic mixture (based on v100 parts by weight phenol,

about 10 to parts by weight about 15 to 55 parts by weight L6 On aweight percent basis when in a form substantially free of othermaterials.

The properties of a given so-substituted phenol product are affected bythe process conditions used to make that product e.g. molecular weightdistribution, color, and the like). The resulting reaction product is,as those skilled in the art will appreciate, a complex mixture ofvarious different substituted phenols produced from the reaction ofphenol under Friedel- Crafts conditions with the carbocyclic compoundstarting mixture to produce phenol molecules which are substituted bothon ring carbon atoms and on phenol hydroxyl oxygen atoms by moietiesderived from such carbocyclic compound.

A substituted carbocyclic compound phenol product can be prepared in aform substantially free of starting materials by conventionaldistillation separation techniques (e.g. steam distillation, vacuumstripping, and the like), as those skilled in the art will appreciate,but in making resoles for use in this invention, such product can beused directly as made.

In general, to produce a resole for use in this invention, a substitutedphenol product, as just described, is neutralized under aqueous liquidphase conditions as by the addition of base (ammonium hydroxide and/oramine), and then from about 0.8 to 2.0 mols of formaldehyde per 1 mol ofphenol (preferably from about 1.0 to 1.5 mols formaldehyde per mol ofphenol) is mixed with the substituted phenol product (now itself astarting material). Water may be added with the formaldehyde. Formalinis preferred as a source for formaldehyde. Also, a basic catalystmaterial, such as ammonium hydroxide and/or amine selected from thegroup consisting of primary amines (such as ethylamine, isobutylamine,ethanol amine, cyclohexylamine, and the like); secondary amines (such asdiethanol amine, piperidine, morpholine, and the like); and tertiaryamines (such as hexamethylene tetramine, triethylamine, triethanolamine,diethyl cyclohexyl amine, triisobutyl amine; and the like) is introducedinto the reaction mixture. Preferred amine catalysts have molecularweights below about 300 and more preferably below about 200. The aminecatalyst may include hydroxyl groups which tend to promote solubility ofthe amine in the reaction mixture. This basic catalyst itself thus canbe used to neutralize the starting substituted phenol. The pH of thisreaction mixture is maintained from (7.0 and preferably above about 7.5)but below about 8.5. This reaction mixture is then heated totemperatures of from about 60 to 100C. for a time sufficient tosubstantially react most of the formaldehyde and thereby produce adesired resole product. Times of from about 20 to 140 minutes aretypical. Aqueous liquid phase preparation conditions are used.

It will be appreciated that the formaldehyde to phenol mol ratios hereindescribed have reference to the total amount of phenol present before areaction, including the phenol which is substituted by the carbocycliccompound mixture, as described above.

To optimize electrical properties in resoles used in this invention, itis preferred to use as a basic catalyst, when reacting such substitutedphenols with formaldehyde to make resole resins, one which is non-ionicand non-metallic in character.

The resole product produced by reacting the substituted phenol withformaldehyde as described above is one composed of methylolatedsubstituted phenol which has been methylolated by the formaldehyde to adesired methylol content and optionally advanced (e.g. the molecularweight of the methylolated substituted phenol increased) as by heatingas necessary or desirable to make a resole resin product havingmolecular weight characteristics as above indicated. As those skilled inthe art fully appreciate, the methylol content and the degree ofadvancement are readily controllable, so that one can optimize such aresole resin for use in a particular application. For purposes of thisinven' tion, a phenol-formaldehyde resole resin or resole can beregarded as being the reaction product of the above describedsubstituted phenol mixture and formaldehyde under the aqueous basecatalyzed conditions as described herein which product can be thermosetby heat alone without the use of a curing catalyst.

In general, such a resole product as made is a brown colored, unstable,multiphase aqueous emulsion whose viscosity depends, in any giveninstance, upon process and reactant variables, but which usually rangesfrom a syrupy liquid to a semi-solid state. Such a resole productusually separates from such aqueous phase as a brown colored materialwhose viscosity varies from a syrup to a solid.

To make a resole resin varnish of this invention such as an emulsion isdehydrated, preferably under heat and reduced pressure, to a watercontent of from about 0.5 to weight percent (based on total resoleweight). When the resulting water content is over about 2 weightpercent, there is produced a simple-phased,

clear dark-colored high solids, resole resin. In any given instance, itstotal solids content, (residual) water content, and viscosity dependupon the amount of substituted phenol aldehyde product present, the molratio of formaldehyde to substituted phenol, specific type and amount ofmethylolation catalyst, conditions and reactants used to substitute thephenol, methylolation temperature, degree of advancement, and the like.

When such a dehydrated liquid resole is further dehydrated to a watercontent under about 2 weight percent, there is produced a solid,so-called one-stage lump resin, which consists substantially of pureresin. Following such dehydration, and, .typically, cooling, this solidresin can be broken up or ground into a solid resin having a convenientparticle size range. Since this one-stage lump resin is heat reactive byitself, it is convenient and preferred to cool it during and towards theend of dehydration so as to slow reaction with itself and therebyprevent gelation. This material is characteristically a dark solid,having a softening point somewhere in the range of from about 25 to100C. or even higher.

After such dehydration, the resulting resole resin is then dissolved ina relatively volatile, inert organic solvent medium having properties asdefined above. It is not necessary, and it is preferred not, to preparethe resole resin in the form of a one-stage lump before dissolutionthereof in such organic solvent.

While the organic liquid used has properties as indicated above, it willbe appreciated that such liquid can comprise mixtures of differentorganic liquids. Preferred liquids are lower alkanols (such as ethanoland methanol) and lower alkanones (such as acetone or methyl ethylketone). The term lower" refers to less than seven carbon atoms permolecule as used herein. Aromatic and aliphatic (includingcycl'oaliphatic) hydrocarbons can also be employed as solvents for agiven resin, including benzene, toluene, xylene, naphthalene, nonone,octane, petroleum fractions, etc. Preferably, the total water content ofa varnish of the invention is below about 10 weight percent, and morepreferably falls in the range of from about 0.5 to 5 weight percent.

Those skilled in the art will appreciate that care should preferably betaken to use an organic liquid system in which the phenolic resoleresins are completely soluble as well as any water present. Adding, forexample, a ketone or an ether-ester solvent like butyl cellosolve willgenerally improve the water tolerance (ability to dissolve water) of asolvent system.

These varnishes are characteristically dark colored, one-phase, clearliquid solutions, each having a viscosity ranging from about 5 to 5,000centipoises. The exact viscosity of a given varnish depends upon manychemical process and product variables. For impregnating applications,viscosities of from about 50 to 500 centipoises are preferred.

The total solids content of a given varnish product can be as high asabout weight percent or even higher, and as low as about 20 weightpercent or even lower, but preferred solids contents usually fall in therange of from about 25 to 65 weight percent. As those skilled in the artwill appreciate, the varnishes of this invention can be advanced (e.g.crosslinked as by heating to produce larger molecules) to a greaterextent without forming precipitates from the organic solvent phase thanis the case of corresponding aqueous resole products.

When used for impregnation and reinforcing purposes, the liquid resoleresin varnishes of this invention are useful for impregnating cellulosicpaper, asbestos paper, and other non-woven sheet structures as well aswoven fabrics (cotton, glass fibers, nylon, etc.), etc. Impregnation canbe accomplished by any convenient means, including dipping, coating,spraying, mixing, or the like. The so-impregnated material is dried tolower the volatiles content and then heated to advance the resin to theproper degree for the intended use. The resole varnishes of thisinvention are useful in the preparation of laminates, such as those madefrom such impregnated sheet materials. Such laminates are used inelectrical applications as supports or as insulation for conductiveelements. The laminates are generally manufactured in a sheet or blockform which is then punched or otherwise machined to provide desiredconfigurations for a particular end use.

The resole varnishes of this invention are also useful in themanufacture of cloth laminates, and automotive oil filters. A suitableoil filter media, for example, is prepared by impregnating with avarnish of this invention, cellulosic fiber paper modified with asynthetic fiber (polyester, or the like) and having a thickness of fromabout to mils. Sufficient resole varnish resin of this invention is usedto obtain an impregnated sheet member having a cured resin content ofabout 15 to percent, based on the weight of the paper. After such paperis so impregnated, it is heated to advance the resin to a so-calledB-stage, and then is corrugated or pleated to form the filter element.The filter element is then assembled with the end use filter containerand heated to 250 to 350F. for from 5 to 20 minutes to cure the resin.When cured, the product has good flexibility and low tendency to crackduring use.

In general, a varnish of the present invention can be used to makereinforced plastics.

Ina more preferred embodiment of the present invention, an organicsolution or varnish contains from about 55 to 65 weight percent (totalsolution basis) of the dissolved phenolic resin. In such a morepreferred solution, there are from about 2 to ,l 2 parts of dissolvedwater (total solution basis). In this invention, all solids areconveniently measured using the ASTM Test Procedure D-l l5-55.

Also in such a preferred embodiment, the substituted phenol used inmaking phenolic resin is made using a carbocyclic compound mixture inwhich there are from about 20 through 40 weight percent of compoundshaving the indene nucleus (as above described), from about 15 throughweight percent of compounds having the dicyclopentadiene nucleus (asabove described) and from about 30 through 65 weight percent ofcompounds having a phenyl group and a vinylidene group (as abovedescribed), the percentage of divinyl benzene in such preferredcarbocyclic compound mixture being as described above, and there being atotal of 100 weight percent of these three components in a given suchcarbocyclic compound mixture when such is in a form substantially freeof other materials.

The term vinylidene as used herein has generic reference both tovinylidene radicals (CI-I C and vinyl radicals (CI-I CH- or -CI-I CH);ob-

serve that in carbocyclic compound mixtures used in this inventionhaving a phenyl group substituted by a vinylidene group, alpha-methylsubstitution is included in this definition, as well as styrene, methylstyrene, and ethyl styrene.

When dehydrating a resole resin made from a substituted phenol asdescribed above and formaldehyde, convenient reduced pressures rangefrom about 5 to 10 psia to an end temperature of about 60 to 90C. thoughthose skilled in the art will appreciate that lower and higher suchpressures and temperatures can be used without departing from the spiritand scope of this invention.

EMBODIMENTS The following additional examples are set forth toillustrate more clearly the principles and practices of this inventionto one skilled in the art, and they are not intended to be restrictivebut merely to be illustrative of the invention herein contained. Unlessotherwise stated herein, all arts and percentages are on a weight basis.

EXAMPLE 1 Charge 100 parts of phenol and 1 part of concentratedsulphuric acid to a suitable reaction vessel and heat the mixture to 50C. Add parts of a carbocyclic compound mixture available commerciallyunder the trade designation Resin Oil from Monsanto Company, having acomposition as given above to the starting mixture while keeping thetemperature stable at 50C. Hold the temperature of the mixture at 50C.after addition of such carbocyclic compound mixture for 1 hour and thenadd 7.5 cc. of 28 percent NI-I OI-I thereto to neutralize the acidcatalyst. To the neutralized reaction mixture, add 2 parts oftriethylamine and 60 parts of 50 percent formalin (50-50formaldehyde-water). Now heat the reaction mixture to a reflux at 100 C.and continue refluxing for 4 hours. Then cool the reaction mixture andremove volatile material under a vacuum of 28 inches of mercury untilthe temperature of the mixture rises to C. Then add 50 parts of methanoland 10 parts of acetone to form a solution having 71.5 percent solids(measured by heating 1% grams of resin for 3 hours at 135C.), an Ostwaldviscosity of 4,582 centipoises at 25C., pH of 8.42 and a water contentof 1.76 percent.

EXAMPLE 2 Charge parts of phenol and 0.1 part of BF to a suitablereaction vessel and heat the mixture to 50C. Add 30 parts of thecarbocyclic compound mixture used in Example 1 to the mixture graduallyover a period of 30 minutes. Hold the temperature of the mixture at 50C.after addition of the carbocyclic compound mixture for 1 hour and thenadd 7.5 parts of 28 percent NH OH to neutralize the acid catalyst. Thenadd 2 parts of triethylamine and 60 parts of 50 percent formalin to theneutralized mixture. Now heat the reaction mixture to a reflux at 100C.and continue refluxing for 2 hours. Cool the mixture and remove volatilematerial (mainly water) under a vacuum of 28 inches of mercury until thetemperature of the mixture rises to 80C. Then add 50 parts of methanolto form a solution having a solids content of 68.5 percent and a pH of8.62.

EXAMPLE 3 Charge 100 parts of phenol and 1 part of concentratedsulphuric acid to a suitable reaction vessel. Add 50 parts of thecarbocyclic compound mixture used in Example 1 to the mixture graduallyover a period of minutes. The temperature of the reaction mixture risesdue to the exothermic reaction. Hold the temperature of the reactionmixture at 75C. for 30 minutes and then add 7.5 parts of 28 percent N1-1O1-1 to neutralize the acid catalyst. Then add 2 parts of triethylamineand 60 parts of percent formalin to the neutralized mixture. Now heatthe mixture to a reflux at 100C. and continue heating the mixture for 2hours. Cool the mixture and remove volatile material under a vacuum of28 inches of mercury until the temperature of the mixture rises to 80C.Then add parts of methanol to form a solution having a solids content of68.5 percent and a pH of 8.62.

EXAMPLE 4 TABLE 111 NEMA Laminate XXXP Water Absorption, 1.0 0.33Dielectric Constant (ASTM D-I 50-S4T) at 10 cps A 4.6 4.25 at 10 cps D24/23 4.8 4.34 Dissipation Factor (ASTM D-l50-54T) at 10 cps A .035 .031at 10 D 24/23 .035 .032

The electrical properties of the resins of this invention are well belowthe maximum NEMA specifications for XXXP type laminates.

EXAMPLES 5 THROUGH 31 The following Examples are presented in tabularform for brevity. The process in all instances is as shown in Example 1except that the indicated variables are altered as shown in Table IVbelow in each respective instance.

This intermediate product in each example is reacted with formaldehydein the manner as taught in Example l to produce first an aqueous resoleemulsion product which is then treated in the same manner as taught inExample 1 to reproduce a resole varnish.

TABLE IV Phenol Type Carbocyelic compound mixture Amount CatalystTcrnperreaction Amount Typo parts) and triethylamine (5 parts) ischarged to a vessel. After reacting at 70 C. until the mixtures freeformaldehyde content is less than 4 percent, the mixture is cooled.About 55 percent solids is obtained.

Eight plies of the so-pre-impregnated paper are then impregnated to atotal resin content of 62 percent with the resin solution of Example 1.The impregnated papers are dried for 19 minutes at C. The 8 plies ofdried impregnated paper are assembled into a deck and cured for 30minutes at C. under a pressure of 1,000 psi to form a laminate aboutone-sixteenth inch thick.

Various properties of the laminates along with, for comparison purposes,the National Electrical Manufacturers Association (NEMA) specificationsthereof for XXXP type laminates are given below in Table 111.

A B C D styrene l-2 10.1 1 10 alpha-methyl styrene 1-3 2.2 2 2beta-methyl styrene l-3 2.1 2 2 vinyl toluene 14-21 10.5 10 25 C alkylstyrene 4-7 5.8 4 4 divinyl benzene 1-2 1.6 l 1 indene 15-22 12.7 25methyl indene 4-7 7.6 5 5 dicyclopentadiene 12-18 1.1 5 25methylcyclopenta- 4-6 2. 1 l 1 diene inert diluent 25-35 44.2 59 0 Thecolumns designated, respectively, Phenol", Amount Carbocyclic CompoundMixture", and Amount Catalyst are in terms of parts by weight.

EXAMPLE 32 Charge 100 parts of phenol and 0.3 part of concentratedsulphuric acid to a suitable reaction vessel and heat the mixture to70C. Add 70 parts of carbocyclic compound mixture used in Example 1 tothe mixture over a period of 45 minutes while keeping the temperature at70-80C. Hold the temperature of the mixture at 70-80C. after addition ofthe carbocyclic compound mixture for minutes. Then add 3 parts ofhexamethylene tetrarnine, 2 parts of triethylamine and 60 parts of 50percent formalin (50,-50 formaldehydewater) to the reaction mixture. Nowheat'thereaction mixtureto atmospheric reflux at 100C. and continuerefluxing for 2.5 hours. Then cool and remove volatile material under avacuum of 25.5 inches of mercury until the temperature of the mixturereaches 60C. Then add 87 parts of methanol to form a solution having59.3 percent solids (measured by heating 1.5 grams of resin for 3 hoursat 135C.) and an Ostward viscosity of 137 centipoises at 25C.

, EXAMPLE 33 Charge 100 parts of phenol and 1 part of concentratedsulphuric acid to a suitable reaction vessel and heat the mixture to50C. Add'50 parts of carbocyclic compound mixture used in Example 1 tothe mixture over a period of 30 minutes while keeping the temperaturestable at 50C. After addition of the carbocyclic compound mixture, add7.5 cc. of 28% Nl-LOH to neutralize the acid catalyst. To theneutralized reaction mixture add 2 parts of triethylamine and 60 partsof 50 percent formalin (50-50 formaldehyde-water). Now heat the reactionmixture to a reflux at 100C. and continue refluxing for 1% hours. Thencool the reaction mixture and remove volatile material-under a vacuum of28 inches of mercury until a temperature of 80C. is

reached. Then add 50 parts of methanol to the reaction mixture.

EXAMPLE 34 Charge 100 parts of phenol and 1 part of concentratedsulphuric acid to a suitable reaction vessel and heat the mixture to50C. Add 70 parts of carbocyclic compound mixture used in Example 1 tothe mixture over a period of 30 minutes while keeping the temperaturestable at 50C. After addition of the carbocyclic 1 compound mixture, add7.5 cc. of 28% NH 0l-l thereto to neutralize the acid catalyst. To theneutralized reaction mixture add 2 parts of triethylamine and 60 partsof 50 percent formalin (50-50 formaldehyde-water). Now heat the reactionmixture to a reflux at 100C. and continue refluxing for 2 hours. Thencool the reaction mixture and remove volatile material under a vacuum of27 inches of mercury until a temperature of 80C. is

reached. Then add 50 parts of methanol to the reaction mixture.

EXAMPLE 35-PART A Four test laminates are prepared from the resinsolutions of Examples 1, 32-34 and 10 mil electrical grade I cottonlinters paper which has been pre-impregnated to al5 percent resincontent with a commercially-available, low molecular weight liquidphenol-formaldehyde resin.

Each laminate is prepared by impregnating 8 plies of the pre-impregnatedpaper to a total resin content of about 60 percent with one of the resinsolutions of Examples 1, 32-34. The impregnated papers are dried at C.until proper laminating flow is attained. The 8 plies of driedimpregnated paper are assembled and cured for 30 minutes to 160C. undera pressure of 1,000 psi to form a laminate about one-sixteenth inchthick.

PART B Part A is repeated except thatan electrical grade phenolic resinmodified with cresol is used.

PART C Part A is repeated except that an unmodified phenolformaldehyderesin prepared by heating 100 parts of phenol in the presence of 1 partBF at 50C. for 1.5 hours and then adding 60 parts of 50 percent formalinin the presence of 7.5 cc. of 28% Nl-l Ol-l and 2 parts of triethylamineunder reflux at 100C. for 20 minutes, is employed in place of thecommercial electrical grade cresol-based resin.

Various properties of the test laminates prepared above along with theNational Electrical Manufacturers Association specification for XXXPlaminates, are given in Table V.

L6 ASTM TEST D--54T The above data show improvements in electricalproperties of modified phenolic resins made in accordance with thisinvention over those of a cresol modified electrical grade phenolicresin or a standard phenol-based resin. Furthermore, the electricalproperties of the resins of this invention are well below the maximumNEMA specifications for XXXP type laminates.

EXAMPLE 36 Charge 100 parts of phenol and 0.3 parts concentratedsulfuric acid to a suitable reaction vessel and reflux at 100C. andcontinue the refluxing for 1.5

hours. Then cool and remove volatile material under a vacuum of mercuryuntil the temperature of the mixture reaches 60C. Then add a 92/8mixture of ethanol/toluene to form a solution having 66 percent solids.

EXAMPLE 37 Two sheets of cellulose fiber paper containing l2 percent ofa synthetic fiber (polyester) and having a thickness of mils areseparately impregnated with -the varnish of Example 36. The impregnatedsheets are heated to B-stage the resin and reduce the volatiles to from4 to 10 percent. The filters are cured for about minutes at about 300F.The following Table VI data shows good strength yet good flexibility inoil filter paper impregnated with a varnish of this invention.

TABLE VI Cured Resin Green Tensile No. of l80 Content Strength FlexesVarnish Volatiles Lbs./ln to rupture Example 20.3/8.5 V9.0 190 36 L6 Theforce required to break 1'' wide strips of the impregnated paper atB-stage. L6 After 2 hours condi tioning in 300F. oil.

EXAMPLE 38 Charge 100 parts of phenol and 0.3 parts concentratedsulfuric acid to a suitable reaction vessel and heat to 70C. Add 70parts of carbocyclic compound mixture used in Example 1 to the mixtureover a period of 45 minutes while keeping the temperature at 7080 C.Hold the temperature of the mixture at 7080C. after addition of thecarbocyclic compound mixture for 15 minutes; then, add 2 parts ofdiethanolamine and 3 parts ethanolamine and 60 parts of 50 percentformalin to the reaction mixture. Now heat the reaction mixture toatmospheric reflux at 100C. and continue the refluxing for 1.5 hours.Then cool and remove volatile material under a vacuum of mercury untilthe temperature of the mixture reaches 60C. Then, add a 92/8 mixture ofethanol/toluene to form a solution having 66 percent solids.

in each of the foregoing Examples l-38 whenever a liquid aqueous resoleresin is made from a substituted phenol and aldehyde in accordance withthe teachings of this invention there is produced first an aqueousemulsion containing water and methylolated substituted phenol plus someadvanced methylolated materials. When this material is dehydrated byheating under vacuum (the temperature being about 60 to 80C. and thevacuum pressure being about 22 to 28 mm Hg) there is produced when theresidue contains less than about weight percent of water a high solid,

viscous, dark colored, single phase fluid which is one of the resoleproducts of this invention.

When this fluid is further dehydrated under similar conditions with awater content of about 2 weight percent, there is produced a solidone-stage lump resin.

When the afore-indicated emulsion is dehydrated under theafore-indicated heat and temperature reduced pressures, thephenol-aldehyde resin is first reduced to a water content under about 20weight per cent and is thereafter dissolved in, respectively, methanoland ethanol to produce resole varnishes of the present invention.

What is claimed is:

l. A varnish adapted for use in the manufacture of reinforced plasticscomprisingf A. from about 20 to weight percent (total solution basis) ofa dissolved phenol-formaldehyde resole resin;

B. from about 0.5 to 15 weight percent (total solution basis) ofdissolved water;

C. the balance up to weight percent (total solution basis) of any givensolution being substantially an organic liquid which:

1. is substantially inert,

2. boils below about C. at atmospheric pressure,

3. is a mutual solvent for said resole resin and for said water;

D. said resole resin being characterized by:

1. having a formaldehyde to phenol mol ratio of from about 0.8 to 2.0,

2. being substantially insoluble in water but having a viscosity inmethanol solution at 60 weight percent resin solids concentration of notgreater than about 5,000 centipoises, and

3. having a free-formaldehyde content which is less than about 5 weightpercent;

E. said substituted phenol mixture having been prepared by graduallyadding a mixture of carbocyclic compounds to a preheated liquid phasemixture of phenol and Friedel-Crafts acid catalyst maintained in therange from about 25 to 200 C. whereby over a time interval of from about10 minutes to four hours from about 10 to 80 parts by weight of saidmixture of carbocyclic compounds reacts with each 100 parts by weight ofphenol;

F. said mixture of carbocyclic compounds comprising (on a 100 weightpercent basis when in a form substantially free of other materials):

1. from 10 to 40 weight percent (total mixture basis) of compounds eachmolecule of which has: a. the indene nucleus,

b. from nine to 13 carbon atoms, c. as nuclear substituents from 0 to 4methyl groups;

2. from 5 to 70 weight percent (total mixture basis) of compounds eachmolecule of which has: a. the dicyclopentadiene nucleus,

b. from 10 to 13 carbon atoms, 0. as nuclear substituents from 0 to 3methyl groups;

3. from 15 to 65 weight percent (total mixture basis) of compounds eachmolecule of which has: a. a phenyl group substituted by a vinylidenegroup, b. from eight to 13 carbon atoms, c. as substituents from 0 to 3groups selected from the class consisting of methyl and ethyl; 4. fromto weight percent divinyl benzene; 5. wherein the sum total of all suchcompounds in any given such mixture of carbocyclic com- I pounds isalways 100 weight percent;

G. said resole resin having been prepared by first reacting saidsubstituted phenol mixture and said formaldehyde in the presence of abasic catalyst selected from the group consisting of ammonium hydroxide,and organic amines while maintaining a pH in the range from 7 to about8.5 and thereafter dehydrating the resulting aqueous emulsion to a watercontent of from about 0.5 to weight percent.

2. The varnish of claim 1 wherein said carbocyclic compound mixturecomprises:

A. from to 40 weight percent (total mixture basis) of compounds eachmolecule of which has:

1 the indene nucleus,

2. from nine to 13 carbon atoms, I

3. as nuclear substituents from 0 to 4 methyl groups;

B. from 15 to weight percent (total mixture basis) of compounds eachmolecule of which has:

1. the dicyclopentadiene nucleus,

2. from 10 to 13 carbon atoms,

v 3. as nuclear substituents from 0 to 3 methyl groups;

C. from 30 to 65 weight percent (total mixture basis) of compounds eachmolecule of which has:

1. a phenyl group substituted by a vinylidene group,

2. from eight to 13 carbon atoms,

3. as substituents from 0 to 3 groups selected from the class consistingof methyl and ethyl;

D. from 0 to 5 weight percent divinyl benzene;

E. wherein the sum total of all such compounds in any given such mixtureof'carbocyclic compounds is always 100 weight percent.

3. The product of claim 1 made from the reaction product of phenol andsaid mixture of carboxyclic compounds in the presence of an inerthydrocarbon such that, of the combined weight of said mixture ofcarbocyclic compound and said inert hydrocarbon, the inert hydrocarbonportion thereof ranges from about 15 to 70 weight percent thereof.

4. The product of claim 1 made from the reaction product of phenol andsaid mixture of carbocyclic compounds in the presence of an inerthydrocarbon such that, of the combined weight of said mixture ofcarbocyclic compound and said inert hydrocarbon, the inert hydrocarbonportion thereof ranges from about 20 to weight percent thereof.

5. The product of claim 1, wherein the basic catalyst is selected fromthe group consisting of the lower primary, secondary and tertiary aminesof molecular weight below 300.

6. The product of claim 1, made from the reaction product of between 15and 55 parts by weight of carbocyclic compound and 100 parts by weightof phenol.

7. The product of claim 1, wherein the mixture of carbocyclic compoundshas a boiling range from 280 to 420 F.

8. A varnish adapted for use in the manufacture of reinforced plasticscomprising:

A. from about 20 to 85 weight percent (total solution basis) of adissolved phenol-formaldehyde resole resin;

B. from about 0.5 to 15 weight percent (total solution basis) ofdissolved water;

5 hydroxide,

C. the balance up to 100 weight percent (total solution basis) of anygiven solution being substantially an organic liquid which:

1. is substantially inert,

2. boils below about 150 C. at atmospheric pressure,

3. is a mutual solvent for said resole resin and for said water; D. saidresole resin being characterized by:

1. having a formaldehyde to phenol mol ratio of f m b t0.8t 2.0, 2. ingsifii stantially insoluble in water but having a viscosity in methanolsolution at 60 weight percent resin solids concentration of not greaterthan about 500 centipoises, and

3. having a free-formaldehyde content which is less than about 5 weightpercent;

E. said substituted phenol mixture having been prepared by graduallyadding a mixture of carbocyclic compounds to molten phenol containingbetween 0.1 and 1 percent of a Friedel-Crafts acid catalyst maintainedat a temperature in the range from 40 to 125 C. whereby over a timeinterval of from about 10 minutes to four hours from about 15 to 55parts by weight of said mixture of carbocyclic compounds reacts witheach 100 parts by weight of phenol; I

F. said mixture of carbocyclic compounds comprising (on a 100 weightpercent basis when in a form substantially free of other materials):

1. from 20 to 40 weight percent (total mixture basis) of compounds eachmolecule of which has: a. the indene nucleus,

b. from nine to 13 carbon atoms,

0. as nuclear substituents from 0 to 4 methyl groups; I

2. from 15 to 30 weight percent (total mixture basis) of compounds eachmolecule of which has: a. the dicyclopentadiene nucleus,

b. from 10 to 13 carbon atoms, c. as nuclear substituents from O to 3methyl groups; 3. from 30 to weight percent (total mixture basis) ofcompounds each molecule of which has: a. a phenyl group substituted by avinylidene group,

b. from eight to 13 carbon atoms,

0. as substituents from 0 to 3 groups selected from the class consistingof methyl and ethyl;

4. from 0 to 5 weight percent divinyl benzene;

5. wherein the sum total of all such compounds is any given such mixtureof carbocyclic compounds is always weight percent;

G. said resole resin having been prepared by first reacting saidsubstituted phenol mixture and said formaldehyde in the presence of abasic catalyst selected from the group consisting of ammonium hydroxide,hexamethylenetetramine, and tri(lower alkyl) amines while maintaining apH in the range from 7 to about 8.5 and thereafter dehydrating theresulting aqueous emulsion to a water content of from about 0.5 to 5weight percent.

9. The product of claim I, wherein the basic catalyst is selected fromthe group consisting of ammonium hexamethylenetetramene andtriethylamine.

2. boils below about 150* C. at atmospheric pressure,
 2. beingsubstantially insoluble in water but having a viscosity in methanolsolution at 60 weight percent resin solids concentration of not greaterthan about 5,000 centipoises, and
 2. from 5 to 70 weight percent (totalmixture basis) of compounds each molecule of which has: a. thedicyclopentadiene nucleus, b. from 10 to 13 carbon atoms, c. as nuclearsubstituents from 0 to 3 methyl groups;
 2. from eight to 13 carbonatoms,
 2. The varnish of claim 1 wherein said carbocyclic compoundmixture comprises: A. from 20 to 40 weight percent (total mixture basis)of compounds each molecule of which has:
 2. from nine to 13 carbonatoms,
 2. from 10 to 13 carbon atoms,
 2. boils below about 150* C. atatmospheric pressure,
 2. being substantially insoluble in water buthaving a viscosity in methanol solution at 60 weight percent resinsolids concentration of not greater than about 500 centipoises, and 2.from 15 to 30 weight percent (total mixture basis) of compounds eachmolecule of which has: a. the dicyclopentadiene nucleus, b. from 10 to13 carbon atoms, c. as nuclear substituents from 0 to 3 methyl groups;3. from 30 to 65 weight percent (total mixture basis) of compounds eachmolecule of which has: a. a phenyl group substituted by a vinylidenegroup, b. from eight to 13 carbon atoms, c. as substituents from 0 to 3groups selected from the class consisting of methyl and ethyl;
 3. havinga free-formaldehyde content which is less than about 5 weight percent;E. said substituted phenol mixture having been prepared by graduallyadding a mixture of carbocyclic compounds to molten phenol containingbetween 0.1 and 1 percent of a Friedel-Crafts acid catalyst maintainedat a temperature in the range from 40* to 125* C. whereby over a timeinterval of from about 10 minutes to four hours from about 15 to 55parts by weight of said mixture of carbocyclic compounds reacts witheach 100 parts by weight of phenol; F. said mixture of carbocycliccompounds comprising (on a 100 weight percent basis when in a formsubstantially free of other materials):
 3. is a mutual solvent for saidresole resin and for said water; D. said resole resin beingcharacterized by:
 3. as nuclear substituents from 0 to 3 methyl groups;C. from 30 to 65 weight percent (total mixture basis) of compounds eachmolecule of which has:
 3. as nuclear substituents from 0 to 4 methylgroups; B. from 15 to 30 weight percent (total mixture basis) ofcompounds each molecule of which has:
 3. as substituents from 0 to 3groups selected from the class consisting of methyl and ethyl; D. from 0to 5 weight percent divinyl benzene; E. wherein the sum total of allsuch compounds in any given such mixture of carbocyclic compounds isalways 100 WEIGHT percent.
 3. The product of claim 1 made from thereaction product of phenol and said mixture of carboxyclic compounds inthe presence of an inert hydrocarbon such that, of the combined weightof said mixture of carbocyclic compound and said inert hydrocarbon, theinert hydrocarbon portion thereof ranges from about 15 to 70 weightpercent thereof.
 3. from 15 to 65 weight percent (total mixture basis)of compounds each molecule of which has: a. a phenyl group substitutedby a vinylidene group, b. from eight to 13 carbon atoms, c. assubstituents from 0 to 3 groups selected from the class consisting ofmethyl and ethyl;
 3. having a free-formaldehyde content which is lessthan about 5 weight percent; E. said substituted phenol mixture havingbeen prepared by gradually adding a mixture of carbocyclic compounds toa preheated liquid phase mixture of phenol and Friedel-Crafts acidcatalyst maintained in the range from about 25* to 200* C. whereby overa time interval of from about 10 minutes to four hours from about 10 to80 parts by weight of said mixture of carbocyclic compounds reacts witheach 100 parts by weight of phenol; F. said mixture of carbocycliccompounds comprising (on a 100 weight percent basis when in a formsubstantially free of other materials):
 3. is a mutual solvent for saidresole resin and for said water; D. said resole resin beingcharacterized by:
 4. from 0 to 5 weight percent divinyl benzene;
 4. Theproduct of claim 1 made from the reaction product of phenol and saidmixture of carbocyclic compounds in the presence of an inert hydrocarbonsuch that, of the combined weight of said mixture of carbocycliccompound and said inert hydrocarbon, the inert hydrocarbon portionthereof ranges from about 20 to 35 weight percent thereof.
 4. from 0 to5 weight percent divinyl benzene;
 5. wherein the sum total of all suchcompounds is any given such mixture of carbocyclic compounds is always100 weight percent; G. said resole resin having been prepared by firstreacting said substituted phenol mixture and said formaldehyde in thepresence of a basic catalyst selected from the group consisting ofammonium hydroxide, hexamethylenetetramine, and tri(lower alkyl) amineswhile maintaining a pH in the range from 7 to about 8.5 and thereafterdehydrating the resulting aqueous emulsion to a water content of fromabout 0.5 to 5 weight percent.
 5. The product of claim 1, wherein thebasic catalyst is selected from the group consisting of the lowerprimary, secondary and tertiary amines of molecular weight below
 300. 5.wherein the sum total of all such compounds in any given such mixture ofcarbocyclic compounds is always 100 weight percent; G. said resole resinhaving been prepared by first reacting said substituted phenol mixtureand said formaldehyde in the presence of a basic catalyst selected fromthe group consisting of ammonium hydroxide, and organic amines whilemaintaining a pH in the range from 7 to about 8.5 and thereafterdehydrating the resulting aqueous emulsion to a water content of fromabout 0.5 to 15 weight percent.
 6. The product of claim 1, made from thereaction product of between 15 and 55 parts by weight of carbocycliccompound and 100 parts by weight of phenol.
 7. The product of claim 1,wherein the mixture of carbocyclic compounds has a boiling range from280* to 420* F.
 8. A varnish adapted for use in the manufacture ofreinforced plastics comprising: A. from about 20 to 85 weight percent(total solution basis) of a dissolved phenol-formaldehyde resole resin;B. from about 0.5 to 15 weight percent (total solution basis) ofdissolved water; C. the balance up to 100 weight percent (total solutionbasis) of any given solution being substantially an organic liquidwhich:
 9. The product of claim 1, wherein the basic catalyst is selectedfrom the group consisting of ammonium hydroxide, hexamethylenetetrameneand triethylamine.